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Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD
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paper135.pdf
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Accepted version
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1.63 MB
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Checksum (MD5)
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Author(s)
Oppenheim, Julius J
Mancuso, Jenna L
Wright, Ashley M
Rieth, Adam J
Hendon, Christopher H
Dincǎ, Mircea
Date Issued
2021
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Oppenheim, Julius J, Mancuso, Jenna L, Wright, Ashley M, Rieth, Adam J, Hendon, Christopher H et al. 2021. "Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD." Journal of the American Chemical Society, 143 (40).
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Author's final manuscript
Abstract
CO, ethylene, and H2 demonstrate divergent adsorption enthalpies upon interaction with a series of anion-exchanged Ni2X2BTDD materials (X = OH, F, Cl, Br; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b][4',5'-i])dibenzo[1,4]dioxin)). The dissimilar responses of these conventional π-acceptor gaseous ligands are in contrast with the typical behavior that may be expected for gas sorption in metal-organic frameworks (MOFs), which generally follows similar periodic trends for a given set of systematic changes to the host MOF structure. A combination of computational and spectroscopic data reveals that the divergent behavior, especially between CO and ethylene, stems from a predominantly σ-donor interaction between the former and Ni2+ and a π-acceptor interaction for the latter. These findings will facilitate further deliberate postsynthetic modifications of MOFs with open metal sites to control the equilibrium selectivity of gas sorption.
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DOI of Published Version
10.1021/JACS.1C07449
